Polymers with antimicrobial, bioresistant and fungal resistant properties

ABSTRACT

A polymer that contains an antimicrobial, bioresistant and fungal resistant moiety that is linked into the backbone of the polymer. The moiety is a bromine atom and a nitro group linked to one or more of the carbon atoms forming the backbone. The moiety can appear in the polymer chain in various levels of occurence from 5 ppm to has high as 100% with a normal occurance of between 1000 ppm to 20,000 ppm. Polymer types that can be created with this moiety to display these properties include, but are not limited to, polyurethane, polyurea, polyamide, polyester, polycarbonate, polyether, polysiloxane, epoxy, polyacrylic, polyacrylate, polyvinyl.

[0001] This application is related to, and claims priority from, U.S.Provisional application No. 60/351,620 filed Jan. 24, 2002 and herebyincorporates that application by reference. This application is alsorelated to, and claims priority from, U.S. Provisional application No.60/361,448 filed Mar. 21, 2002 and hereby incorporates that applicationby reference. This application is also related to, and claims priorityfrom, United States Provisional patent application No. 60/392,007 filedJun. 26, 2002 and hereby incorporates that application by reference.This application is also related to and claims priority from UnitedStates provisional patent application 60,411,907 filed Sep. 18, 2002 andhereby incorporates that application by reference. This application alsoclaims priority from German patent application DE 202 11 854 filed Aug.1, 2002.

FIELD OF THE INVENTION

[0002] The present invention relates to the field of polymers and paintscontaining polymers and more particularly to polymers with bioresistant,fungal resistant and antimicrobial/antifungal properties.

DESCRIPTION OF THE PROBLEM SOLVED BY THE INVENTION

[0003] Due to environmental regulation, the use of tin, mercury, lead,and other heavy metals in coatings is illegal in most of the developedworld. In particular marine coatings and paint suffer a failure modewhen attacked by microbes. The problem is especially acute in thatsection of the hull of a vessel that is alternately submerged andexposed to air. Microbial attack can eventually destroy the coatingcompletely. Previously, heavy metals were used in coatings to combatthis attack.

[0004] Some methods have been devised that distribute an oil-solubleantimicrobial agent in the coating, relying on the water insolubilityand limited mobility of the agent in the coating to hold the agent.However, it is well known that all liquids, and to a lesser extent allsolids, are either somewhat soluble in water, or can be absorbed orleached into water to some extent. After repeated cycles of beingsubmerged and exposed, the agent is sufficiently leached from thecoating rendering the coating susceptible to microbial attack; hence thecoating becomes ineffective. One solution to the leaching problem hasbeen to create a coating that is sacrificial and is designed to wearaway as it ages, exposing fresh antimicrobial agent to the surface. Herethe life is proportional to coating thickness. Thick coatings arehowever a problem in marine coatings as they increase the weight andcost of the coating.

[0005] The painting of the hull of a marine vessel is a very expensiveand cumbersome operation because the vessel must be drydocked. This isexpensive in itself, and costs increase because of the length of timethe vessel must be out of service. Thus, any means of extending theprotective coating's life has great economic impact.

[0006] What is badly needed is a polymer type coating that hasbioresistive, fungal resistive or antimicrobial/antifungal propertiesthat can be used in paints and in other applications of polymers whereit is desired to prevent microbial attack of the polymer and/or preventthe polymer from acting as a substrate and/or food source for bacteria,and/or fungi, or can kill microbes directly.

[0007] It is also believed that polymers of the type described in thisinvention will aid in the adhesion of the polymer to various substrateswhen used as part of a coating or adhesive.

SUMMARY OF THE INVENTION

[0008] The present invention comprises a polymer that contains anantimicrobial moiety that is linked into the backbone of the polymer.This moiety is, in general, a bromine atom and a nitro (NO2) grouplinked to one or more of the carbon atoms forming the backbone of thepolymer. While the present invention is directed primarily to urethanetype polymers, the moiety taught should also be effective when linkedonto a carbon atom in the backbone of any polymer. The moiety can appearin the polymer chain in various levels of occurrence. A preferredoccurrence of around 1000 parts per million to around 20,000 parts permillion is effective. However the frequency of occurrence can be as lowas 5 parts per million to as high as 100%. Polymer types within thescope of the invention include, but are not limited to polyurethane,polyurea, polyamide, polyester, polycarbonate, polyether, polysiloxane,epoxy, polyacrylic, polyacrylate and polyvinyl linkages.

[0009] It is well known in the art to combine an organic isocyanate witha polyol (poly alcohol) or polyol polymer in the presence of a suitablecatalyst to form a polyurethane polymer. The present invention adds abromo-nitro substituted diol or polyol to a standard polyol to be usedin the polymer synthesis. The proportion of substituted compound used ischosen to yield the desired concentration of the moiety in the finalpolymer. A preferred diol for the application is bromonitropropanediolor 2-bromo-2-nitro-propane-1-3-diol or simply BNPD. This particular diolis a solid material with varying degrees of solubility in other polyolsand has proven antimicrobial properties.

[0010] In addition, BNPD has been shown to have no tetragenecy (cancercausing effects) and is approved by the CFTA at levels of up to 0.1% foruse in cosmetics. BNPD has also been used in baby wipes for itsantimicrobial properties.

[0011] The fact that the active antimicrobial moiety is covalentlylinked directly into the backbone of the polymer prevents it fromleaching out under even very severe conditions of repeated submersionand exposure. In addition, the moiety is not photo-active or decomposedby sunlight or exposure to mineral salts such as sodium chloride asfound in sea water.

[0012] Because BNPD is a substituted diol, it is a natural reactant toform part of a polymeric chain with an isocyanate. Also, being a diol,it mixes directly with a wide range of solvents, polyols and otherperformance enhancing additives with no difficulty or adverse reactions.In fact, it can be mixed in any desired proportion (to the extent thatit is soluble with or without the aid of a solvent or co-solvent) withany standard polyol used in synthesizing polyurethane or other polymers.There also appears to be little ability of the bromine or nitro group toform undesirable cross links in the resulting polymer. BNPD can also beadded directly to an isocyanate or polyisocyanate and heated to thereaction temperature required for the specific isocyanate orpolyisocyanate. If an excess of isocyanate is added in variousproportions, such as 2 equivelents to one, a BNPD containing isocyanateor polyisocyanate results. This product is then an excellent componentto cross-link other polyols or polyamines.

[0013] While bromonitropropanediol (BNPD) is the preferred antimicrobialagent because of its proven activity and its benign effects on theenvironment and on humans, it is clear to one skilled in the art thatother diols or polyols with bromine and nitro groups linked at the sameor different carbon atoms could also be incorporated into the backboneof polymers. Therefore other antimicrobial agents that can be linkedonto a diol or polyol chain are within the scope of the presentinvention.

DESCRIPTION OF THE DRAWINGS

[0014]FIG. 1. Shows the generic steps of forming a polymer with abromine/nitor moiety after removal of water and condensationpolymerization. FIG. 2 and FIG. 2A show the standard method of makingpolymacon as well as two methods of making a modified polymaconcontaining the desired moiety.

[0015]FIG. 3 shows treatment of BNPD with ammonium hydroxide to form abromonitro amine or diamine which can then be combined with anisocyanate compound such as TDI (toluene diisocyanate) to yield apolyurea.

[0016]FIG. 4 shows BNPD used to form a polyester.

[0017]FIG. 5 shows a polyamide structure.

[0018]FIG. 6 shows the standard structure of a polyamide.

[0019]FIG. 7 shows a modified polyether and a modified polysiloxane.

DETAILED DESCRIPTION OF THE INVENTION

[0020] It is well known in the art to combine polyols or polyolpre-polymers with organic isocyanates and other materials to formpolymers and polymer resins. In particular paints, including marinepaint, many times contains polyurethane or other polymer coatingmaterials. A generic urethane has the following structure:

[0021] It is well known in the art that R and R′ can be the same ordifferent. A typical polyurethane polymer is made up of chains of theform:

[0022] or of the form:

[0023] It is also known that the compound bromonitropropanediol or2-bromo-2-nitro-propane-1-3-diol (BNPD) has antimicrobial properties.Tests on this compound have shown that it is effective against variousstrains of both gram positive and gram negative bacteria inconcentrations of 1-50 ppm with the average minimum inhibitoryconcentration being around 25 ppm. In addition, work has indicated thatBNPD is also antifungal.

[0024] BNPD has the following structure:

[0025] Because BNPD is a polyol, it can be combined with other polyol orpolyol pre-polymers to make many polymers and coatings.

[0026] In particular, BNPD mixed polyols can be combined with organicisocyanates to form polyurethane type coatings and polymers. This causesthe active moiety to become covalently linked into the backbone of thepolymer. In particular, BNPD or similar compounds containing the desiredmoiety can be mixed with the polyol component of commercially availabletwo-component systems known in the art. In the case of polyurethane, thelinked moiety is similar to:

[0027] Or more generally:

[0028] While BNPD is a preferred polyol starting point to link theactive moiety into a polymer, it is within the scope of the presentinvention to use many other materials that contain a bromine atom andnitro group linked near one another. The preferred class of compoundshave the bromine and nitro linked to the same carbon atom; however, itis felt that a moiety where the bromine and nitro are not linked to thesame carbon, but near each other will still be effective. Many othercompounds are within the scope of the present invention. In particular,bromonitromethanediol, bromonitroethanediol, bromonitrobutanediol, etc.can also be substituted into polymer backbones with similar results. Theprior art has shown that bromonitromethane is effective for thetreatment of nematodes in the soil (See U.S. Pat. No. 5,013,762) and asa general biocide (See U.S. Pat. No. 5,866,511). It is felt thatbromonitromethanediol and similar diols will be equally effective.

[0029] The present invention also includes using a BNPD or BNPD analogas the terminus, such as:

[0030] Where R′ can be, but is not limited, to CH2OH, OH, CH3, or H. Thepresent invention also includes the presence of BNPD or a BNPD analog asdescribed above as a sidechain as is the case in FIG. 2.

[0031] Methods of making polyurethane coatings for paints are well knownin the art. For example U.S. Pat. No. 5,712,342 gives several examplesof a process for producing a water-dispersion of polyurethane resin fora paint using a prepolymer of approximate molecular weight 800 made fromphenylpropane and various isocyanates such as isophoron-diisocyanate toproduce final polymers with average molecular weights of around 3200 forcoatings used in paint. This patent (U.S. Pat. No. 5,712,342) is herebyincorporated by reference.

[0032] U.S. Pat. No. 3,936,409 teaches a method of manufacturingurea-urethanes using organic solvents. Formation in solution where thesolvent is allowed to evaporate causing a cure, and immediate formationthrough the use of a spray gun are taught. This patent (U.S. Pat. No.3,936,409) is hereby incorporated by reference.

[0033] The present invention dissolves BNPD or similar substitutedhydrocarbon diols into the polyols, with or without the aid of a solventor co-solvent, used to create the prepolymers so that the active moietyof bromine and nitro becomes linked into the backbone of the finalpolymer at an occurrence rate of between 5 ppm up to 100% with apreferred occurrence rate of around 1000 ppm. The molecular weights offinal polymers can range from several thousand for coatings to hundredsof thousands or higher for various other polymers where antimicrobial orantifungal properties are desired.

[0034] U.S. Pat. No. 5,798,115 teaches linking of other antimicrobialagents into the backbone of polymers used in medical applications. Inparticular diisocynates are reacted with an antimicrobial agentciprofloxacin to form polymeric materials. Here a biodegradable polymeris formed that releases antimicrobial substances as it is degraded byenzymes. This patent (U.S. Pat. No. 5,798,115) is hereby incorporated byreference.

[0035] Polymers for the medical industry and many other purposescontaining the active moiety of bromine and nitro linked to an aliphaticchain which is covalently bonded into the polymer backbone for thepurpose of killing microbes or inhibiting degradation caused by microbesor fungus are also within the scope of the present invention. In fact,the present invention finds application wherever a polymer is neededthat has antimicrobial, antifungal, bioresistant or fungal resistantproperties.

[0036] The present invention covalently links a bromine/nitro moietyinto the backbone of a polymer to provide antibaterial or anti-fungaleffect. The general principle taught by the present invention applies topolyurethane, polyurea, polyacrylates, polymethacrylates, polyacrylics,polyesters, polyamides, polyimides, polycarbonates, polyglycolic acid,polylactic acid, polyethers, polysiloxanes, epoxies and many other typesof polymer structures.

[0037] Of particular interest are polymers made from polylactic acid.These polymers have been known in the art since 1932. Lactic acid can bemade commercially by fermenting dextrose from corn. Lactic acidintermediates called lactides are made from L-lactic acid and R-lacticacid. Properties of the final polymers can be controlled by thepercentage of L and R isomer ratios.

[0038] Polylactic acid polymers have the property that they arebiodegradable. Because applications of the present invention includemany applications that may require or desire inhibiting the natural rateof this biodegradation, the present invention applies to this class ofpolymer as well. An example of a polylactic acid polymer using theteachings of the present invention combines lactic acid with BNPD. Apolymer is formed with the bromine/nitro moiety after removal of waterand condensation polymerization. The generic steps are shown in FIG. 1.It should be remembered that the steps shown in FIG. 1 are only genericand that other ways of linking in the bromine/nitro moiety are withinthe scope of the present invention.

[0039] Similar to polylactic acid, polyglycolic acid is of particularinterest. Polyglycolic acid is another biodegradeable polymer that canbenefit from controlling the rate of biodegradation.

[0040] Another class of polymers using the teachings of the presentinvention are polymethacrylate polymers used in contact lenses such aspolymacon.

[0041]FIG. 2 and FIG. 2A show the standard method of making polymacon aswell as two methods of making a modified polymacon containing thedesired moiety. Either methacrylic acid or methyl methacrylate can becombined with BNPD or a similar diol with a bromine and nitro grouplinked to the same carbon atom. Generally 2 moles of methacrylic acidare reacted with one mole of BNPD (however, equamolar quantities canalso be used). The resulting product can then be combined with ethyleneglycol dimethacrylate (2-Hydroxyethyl Methacrylate). Ethylene glycolmonomethacrylate can also be added to reach the desired properties.

[0042] U.S. Pat. No. 4,109,074 teaches the basic process for making thistype of hydrophilic polymer from the monomer. The basic polymer isprepared by heating a monomer such as ethylene glycol monomethacrylateto a certain temperature for a certain time. No initiator or catalyst isused in the original process. This has the desirable property ofyielding a polymer that is immediately free of any toxic residue from aninitiator or catalyst. This is particularly desirable in medicalproducts such as contact lenses. This patent (U.S. Pat. No. 4,109,074)is hereby incorporated by reference.

[0043] A major problem with contact lenses is the danger of bacterialinfection leading to eye irritation or even more serious infections thatcan result in blindness. It would be very desirable to be able toproduce a suitable hydrophilic polymer that inhibits bacterial growth atits surface. The linking of the bromine/nitro moiety as herein taughtcan result in a suitable polymer with the desired bacterial resistantproperties.

[0044]FIG. 3 shows treatment of BNPD with ammonium hydroxide to form abromonitro amine or diamine which can then be combined with anisocyanate compound such as TDI (toluene diisocyanate) to yield apolyurea. FIG. 3 shows two possible structures that are within the scopeof the present invention, one with two nitrogens linked to a carbonylgroup and one with only one.

[0045]FIG. 4 shows BNPD used to form a polyester, while FIG. 5 shows apolyamide structure. FIG. 6 shows the standard structure of thepolyamide known as Nylon Sixty-Six (NYLON is the registered trademark ofDuPont Corp.). The modified polyamide structure containing thebromine/nitro moiety is clearly seen. It should be understood that theall polyamides are within the scope of the present invention.

[0046]FIG. 6 shows a modified epoxy resin while FIG. 7 shows a modifiedpolyether and a modified polysiloxane. Both of these classes ofstructures are within the scope of the present invention. Again, allpolyethers and polysiloxanes are within the scope of the presentinvention.

[0047] The invention relates to a bromo-nitro moiety covalently linkedinto the backbone of various polymers in order to provide bacterial andfungus resistance or antibacterial/antifungal polymers of many differentcategories and types. The invention has many useful industrialapplications.

EXAMPLES Example 1 Urethane

[0048] 6 g BNPD were desolved in 14 g γ-Butyrolacton (BLO) with strongmixing. In these 100 g urethane quality castor-oil was added also withstrong mixing. Then into this mixture, 42 g aromatic isocyanate BayerMondur XP-744 was added drop by drop over twenty minutes, followed anadditional 20 minutes of strong mixing. This prepolymer urethane of thecastor-oil/BNPD can be called T-31BR.

[0049] To 39 g of Chemoddities HP70 acryl polyole, 0.12 g Eagle Sales FB100 Defoamer, and 0.12 g Eagle Sales FX-6 slip Aid were added 15 gT-31BR. This mixture can be called componet I. To componet I was added11 g Bayer Mondur XP-744 flavour TIC isocyanate prepolymer and 10 g BLO.The BLO was to improve flow. A sample was taken off as film, which wasan excellent clear urethane layer.

[0050] The acrylic urethane layer contained 0.85% BNPD.

Example 2 Urethane

[0051] 150 g of BNPD was dissolved in 150 g BLO. To 150 g of thissolution was added 270 g Bayer Mondur XP-744 and heated to 150 F andheld for 30 minutes. The BNPD containing isocyanate functionalcross-linker was allowed to cool to room temperature.

[0052] To 25 g of the BNPD containing isocyanate cross-linker was added30 g Chem-oddities HP70 acrylic polyol with strong mixing. This wasdrawndown to yield a clear, tack free urethane film that contained 9.9%BNPD.

Example 3 Urethane

[0053] 10 g of BNPD was dissolved in 15 g BLO. To this solution wasadded 18 g Bayer Mondur XP-744 and mixed. To this solution was added 0.1g Troymax 16% Zinc catylst. As soon as heat was seen to be evolved, themixture was drawndown. The resulting, tack-free urethane film contained35.7% BNPD.

Example 4 Urethane

[0054] 10 g of BNPD was added directly to 18 g Bayer Mondur XP-744 andheated to 230 F and held for 30 minutes. The resulting product wasdrawndown and yielded a clear tack-free urethane film that contained35.7% BNPD.

Example 5 Acrylate Resin

[0055] 400 g (2 mol) BNPD with 344 g (4 mol) methyl methylmethacrylateand 150 g xylene (reflux solvent) was combined in a nitrogen coveredreaction vessel with a water condenser/trap. The mixture was heated to141 degrees C., at which time trapped water was released. The reactionvessel has held between 154-156 degrees C. until the rate of the waterloss was nearly zero. (3 hours and 7 minutes). The theoretical loss ofwater was 72 g. 53 g was recovered, and approximately 19 g unreactedBNPD was left in the reaktion vessel. The unreacted BNPD was removed.This conversion product can be called MAA/BNPD-002.

[0056] Then 360 g xylene were added to a reaction vessel with agitation.The container had a nitrogen blanket and a water condenser/trap, and washeated to 141 degrees C. To this, drop by drop, over 3 hours, 20 gMAA/BNPD-002 was combined with 598 g Isobutylmethacrylate and 20 g TertButylperoxybenzoate were added. After adding was complete, the containerwas held at 142 degrees C. for 55 minutes. Then 2 g of TertButylperoxybenzoate in 18 g Xylene were added, and the mixture was heldat 142 degrees C. for one hour. Then 2 g more of TertButylperoxybenzoate in 18 g Xylene were added, and again the mixture washeld at 142 degrees C. for one hour. Finally 6 g TertButylperoxybenzoate were added, and the mixture was held at 142 degreesC. again for one hour. Then the container was removed from the heat andleft to cool.

[0057] The resulting polymer had a color of bright straw, with enoughtransparency to be used as a clear coat. The material was drawn out toconfirm this. This resin contains 924 ppm BNPD.

Example 6 Polyester Resin

[0058] In a reaction vessel with a nitrogen blanket and watercondenser/trap 400 g (2 mole) BNPD were mixed with 616 g (4 mole)1,2-Cyclohexandicarboxlic anhydride (HHPA) and 150 g Xylene as areaction solvent and heated with agitation.

[0059] The container was heated to 162 degrees C., at which point thereaction became exothermic. The temperature was then reduced to 150degrees of C and held for one hour 1162 g of a conversion product, astrong, dark transparent liquid, was recovered. This conversion productcan be called MAA/BNPD-003.

[0060] In a reaction vessel with a nitrogen blanket and watercondenser/trap 416 g Neopentylglycol (NPG) and 1,7 g HHPA/BNPD-003 washeated with agitation. The container was heated until the NPG began tomelt. Stirring turned on and the temperature held at 149 degrees C. forone hour and 38 minutes. Then 438 g of Adipic acid were added to thecontainer, and after two minutes water started to be released.

[0061] The container was then held between 156 degrees C. and 172degrees C. for 3 hours, until the release of the water stopped and thetemperature began to rise. A total quantity 108 g water was released.The resulting resin has a brownish color and was very clear andtransparent. It contained 896 ppm BNPD.

Example 7 Diester n=1

[0062]

[0063] 1,128 g oleic acid and 400 g BNPD plus 2 g sulfuric were chargedin a three neck round bottom flask with agitation, nitrogen, andcondenser and heated to 350 F and held for 2.5 hrs until 80 ml of waterwere recovered. This product was then incorporated into EngineeredLubricants Encool SS at 6% and 10% of the concentrate.

[0064] These samples were then submitted for ASTM D-3946-92 testing. Thesamples at day 5 were compared and the sample with 6% incorporation hada bacterial count of 1.5×10⁴ and the sample with 10% incorporation had abacterial count of 3×10³ versus 1×10⁷ for the sample without the productincorporated.

I claim:
 1. A polymer containing a bromo-nitro group having the formula:

where R and R′ are the same or different and are independently chosenfrom the group containing-linear or branched, saturated or unsaturated,alkyl, alkenyl, alkylamine, —NH—, —NR—, or arylalkyl with 0 to 10 carbonatoms and where A and A′ are the same or different and are independentlychosen from the group containing [—(C═O)O—, —O(C═O)NH—, —HN(C═O)NH—,—O—, —OH, —CH₂OH, —CH₃, —(C═O)OH, —O((C═O)CO)_(m)—, —O((C═O)C═C)_(m)—,—N(C═O)—, —O(C═O)C₆H₄(C═O)—, —O(C═O)D-, —OC(C—OH)D-, —(O—SiH₂)_(m)—,—(CH₂)₁—] where D is linear or branched, saturated or unsaturated,alkyl, alkenyl, alkylamine or alkylaryl with 0 to 10 carbon atoms, andwhere 1 and m are integers greater than zero.
 2. A polymer according toclaim 1 wherein A and A′ are the same or different and are independentlychosen from the group containing [—(C═O)O—, —O(C═O)NH—, —HN(C═O)NH—,—O—, —OH, —CH₂OH, CH₃, —(C═O)OH, —O((C═O)C═C)_(m)—, —N(C═O)—,—(O—SiH₂)_(m)—, —(CH₂)_(m)—] wherein m is an integer greater than zero.3. The polymer of claim 1 wherein the bromo-nitro group has anoccurrence rate of from 5 ppm to 100%.
 4. A surface coating comprising apolymer according to claim
 1. 5. A cast part comprising a polymeraccording to claim
 1. 6. An extruded film or fiber comprising a polymeraccording to claim
 1. 7. A polymer comprising at least one bromo-nitrogroup covalently bonded, said polymer having the formula:

where R and R′ are the same or different and are independent chosen fromthe group containing [—(C═O)O—, —O(C═O)NH—, —HN(C═O)NH—, —O—, —OH,—CH₂OH, CH₃, —(C═O)OH, —O((C═O)C═C)_(m)—, —N(C═O)—, —(O—SiH₂)_(m)—,—(CH₂)_(n)—] where m is an integer greater than zero.
 8. A surfacecoating comprising a polymer according to claim
 7. 9. A cast partcomprising a polymer according to claim
 7. 10. An extruded film or fibercomprising a polymer according to claim
 7. 11. The polymer of claim 7wherein the occurrence rate of the bromine and nitro group is between 5ppm and 100%.
 12. A polymer comprising at least one bromo-nitro group ofthe formula:

wherein R an R′ are the same or different and are independently chosenfrom the group containing [(C═O)O—, —O(C═O)NH—, —HN(C═O)NH—, —O—, —OH,—CH₂OH, CH₃, —(C═O)OH, —O((C═O)C═C)_(m)—, —N(C═O)—, —(O—SiH₂)_(m)—,—(CH₂)_(m)—] where m is an integer greater than zero.
 13. A surfacecoating comprising a polymer according to claim
 12. 14. A cast partcomprising a polymer according to claim
 12. 15. An extruded film orfiber comprising a polymer according to claim
 12. 16. The polymer ofclaim 12 wherein the occurance rate of the bromine and nitro group isbetween 5 ppm and 100%.
 17. A polymer comprising at least onebromo-nitro group covalently bonded of the formula:

wherein R and R′ are the same or different and are independently chosenfrom the group containing [—(C═O)O—, —O(C═O)NH—, —HN(C═O)NH—, —O—, —OH,—CH₂OH, CH₃, —(C═O)OH, —O((C═O)C═C)_(m)—, —N(C═O)—, —(O—SiH₂)_(m)—,—(CH₂)_(m)—] wherein m is an integer greater than zero.
 18. A surfacecoating comprising a polymer according to claim
 17. 19. A cast partcomprising a polymer according to claim
 17. 20. An extruded film orfiber comprising a polymer according to claim
 17. 21. A polymercomprising at least one bromo-nitro group covalently bonded of theformula:

wherein R, R′ and R″ are the same or different and are independentlychosen from the group containing [—(C═O)O—, —O(C═O)NH—, —HN(C═O)NH—,—O—, —OH, —CH₂OH, CH₃, —(C═O)OH, —O((C═O)C═C)_(m)—, —N(C═O)—,—(O—SiH₂)_(m)—, —(CH₂)_(m)—] wherein m is an integer greater than zero.22. A surface coating comprising a polymer according to claim
 21. 23. Acast part comprising a polymer according to claim
 21. 24. An extrudedfilm or fiber comprising a polymer according to claim
 21. 25. A polymercomprising at least one bromo-nitro group covalently bonded of theformula:

wherein R, R′ and R″ are the same or different and are independentlychosen from the groups containing: [—CH₂O—, —(CH₂CH₂O)_(m)—,—(CH₂CH(CH₃)O)_(m)—, —(CH₂CH(CH₂CH₃)O)_(m)—] wherein m is an integergreater than zero.
 26. A surface coating comprising a polymer accordingto claim
 25. 27. A cast part comprising a polymer according to claim 25.28. An extruded film or fiber comprising a polymer according to claim25.
 29. A surfactant comprising a polymer according to claim
 25. 30. Apolymer comprising a monomer having at least one bromine atom and atleast one nitro group covalently bonded to the same or different carbonatoms either in a backbone or a sidechain wherein said polymer is areaction product of a polyisocyanate with a polyol, the polyol orpolyisocyanate containing the bromine atom and the nitro group.
 31. Apolymer comprising a monomer having at least one bromine atom and atleast one nitro group covalently bonded to the same or different carbonatoms either in a backbone or a sidechain wherein said polymer is areaction product of a polyisocyanate with a polyamine, the polyamine orpolyisocynate containing the bromine atom and the nitro group.
 32. Apolymer comprising a monomer having at least one bromine atom and atleast one nitro group covalently bonded to the same or different carbonatoms either in a backbone or a sidechain wherein said polymer is areaction product of an epoxide and BNPD or a BNPD containing prepolymer.33. A polymer comprising a monomer having at least one bromine atom andat least one nitro group covalently bonded to the same or differentcarbon atoms either in a backbone or a sidechain wherein said polymer isa reaction product of a polycarboxcylic acid with a polyol, said polyolor polycarboxcylic containing the bromine atom and the nitro group